US3440253A - Method of refining vegetable and animal oils - Google Patents

Method of refining vegetable and animal oils Download PDF

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Publication number
US3440253A
US3440253A US686832A US3440253DA US3440253A US 3440253 A US3440253 A US 3440253A US 686832 A US686832 A US 686832A US 3440253D A US3440253D A US 3440253DA US 3440253 A US3440253 A US 3440253A
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Prior art keywords
oil
refining
acid
salt
aqueous
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US686832A
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Adolf Koebner
Thomas Thornton
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Marchon Products Ltd
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Marchon Products Ltd
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Priority claimed from GB2466562A external-priority patent/GB1002974A/en
Priority claimed from OA52258A external-priority patent/OA01864A/xx
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases

Definitions

  • the present invention relates to an improved method of refining vegetable, animal and marine oils and is a continuation-in-part of our copending application No. 340,804 filed Jan. 20, 1964 and now abandoned, which is itself a continuation-in-part of application No. 290,935 filed June 27, 1963 and now abandoned.
  • Such oils are neutral glyceride esters of fatty acids, but during extraction from their naturally occurring state some degradation of the oil occurs and the resulting crude oil contains free fatty acids dissolved in the oil.
  • the conventional method of refining such oils involves treating the crude oil with an aqueous alkaline solution, such as dilute sodium hydroxide or sodium carbonate, followed by several water washes and, if necessary, by an adsorptive bleaching process using activated earths.
  • a process of deodorisation is also used in which steam or an inert gas is blown through the oil at an elevated temperature under vacuum. In this alkali refining process, the free fatty acids present in the crue oil are removed as soaps.
  • the original glyceride oil contains phosphatides, eg in the case of soya bean oil, we have found that these are extracted into the the aqueous layer and can be recovered therefrom by known methods.
  • the phosphatides e.g. lecithin
  • other polar bodies such as proteins, aldehydes and colouring matter which are more hydrophilic than the glyceride oils but somewhat less hydrophilic than the soaps, are also removed from the oil phase into the aqueous phase. Because of this the oils obtained by our method are substantially equal in quality to oils obtained by conventional refining methods which involve purification in several stages including alkali refining, adsorptive bleaching and de-odorising. By using our method it may be possible in some cases to reduce the number of refining stages to one.
  • the sulphonate salts for use in the invention are defined as monouuclear sulphonates of alkyl aryl sulphonates wherein the aromatic nucleus may contain up to three alkyl substituents, and the total number of carbon atoms of all the alkyl substituents does not exceed four.
  • Such sulphonate salts include for example the alkalimetal or ammonium salts of benzene, xylene, toluene, cymene and cumene sulphonic acids.
  • sulphonate salts which are substantially free from sulphone materials.
  • Such sulphonefree sulphonate salts may be readily obtained in known manner by preparing a crude sulphonic acid by the action of sulphur trioxide on the appropriate hydrocarbon, quenching the reaction mixture, neutralising it with a base and subsequently washing the crude sulphonate salt with the hydrocarbon from which it has been derived.
  • Especially preferred sulphone-free hydrotropes for present use are those sodium xylene sulphonates sold by the applicants under the trademark Halvopon Or.
  • the sulphonate salts for present use do not markedly depress the surface tension of water and are not to be confused with the surface-active sulphonate salts, which contain long chain alkyl substituents.
  • the surface-active sulphonate salts are not suitable for present use since, even when used in minor amounts, they bring about emulsification of the oil and soap layers and render it virtually impossible to recover any oil from the refining mixture.
  • the concentration of the sulphonate salt during refining required to achieve the clean separation of the oil and soap layers will depend upon the salt employed. As a general guide we have found that a concentration of at least 30% by weight is required with most of the sulphonate salts although cumene sulphonates are effective when used in a concentration as low as 25%. There is no upper limit to the concentration of the aqueous sulphonate solution which is employed and saturated solutions may therefore be used. However, the optimum concentration is less than saturation and is usually within the range 40 to 60%. The concentrations referred to above are based on the total amount of water present in the refining mixture.
  • the concentration of the aqueous solution of the sulphonate added to the refining mixture is usually Well in excess of the figures quoted above in order to achieve the desired concentration during refining. In some instances to achieve the desired concentration it may be necessary to add dry sulphonate salt to the refining mixture.
  • the amount of sulphonate salt, as opposed to the concentration of its aqueous solution, required to bring about a satisfactory separation of the oil and soap layers will depend upon the amount of free fatty acid in the crude oil.
  • the use of 2 to 6 times the weight of the free fatty acid in the crude oil usually provides satisfactory results.
  • the alkali used in the refining of the crude oil may be any of the saponifying or non-saponifying alkalis in common use. It is preferred to use sodium hydroxide and/or sodium carbonate.
  • the amount of water present is determined by the amount of and concentration required for the sulphonate salt, with the result that the alkali is usually present initially as a dilute aqueous soltion, for example a 20% solution.
  • the water added to the crude oil in the form of the aqueous alkali must be allowed for when calculating the concentration of the sulphonate solution which is to be added. In some cases it may be necessary to use comparatively concentrated aqueous alkali in order to avoid adding excessive amounts of wateuto the refining mixture.
  • the process of the invention is applicable to the treatment of a large variety of crude oils and has the advantage that it can be used for refining oils which contain more than the normal amount of fatty acids and which would not be worth refining, or would be impossible to refine, by conventional methods owing to the excessive loss of oil or the impossibility of breaking the soap/oil emulsions formed during refining.
  • tallow oils which contain as much as 25 fatty acids, can be refined by the method of our invention with very little loss of glyceride oil.
  • the refining of the crude oil may be carried out in the normal manner.
  • the oil may be admixed with the alkali and subsequently with the sulphonate salt or in the reverse order. More commonly the sulphonate salt and alkali solutions may be premixed and the mixture then fed to the crude oil.
  • the refining mixture is allowed to separate into an upper oil layer and a lower aqueous soap layer.
  • the separation of the layers may be aided by, for example, centrifuging or other mechanical means.
  • glyceride oil may be treated with a further small qauntity of sulphonate salt in aqueous solution and the two layers formed allowed to separate.
  • the second aqueous layer is separated off and may be combined with that originally obtained if desired.
  • the oil layer after a wash with water, is dried under vacuum to obtain substantially pure glyceride oil.
  • the aqueous layer or layers obtained from the refining of the crude oil comprise a solution of the fatty acid soaps in the sulphonate salt solution.
  • the fatty acid values may be recovered from such a solution by treatment with a mineral acid, such as sulphuric acid. Acidification is preferably carried out to give a pH value of from about 4 to about 5. Often the fatty acids, especially if they are of comparatively low polarity, will separate out after acidification to form an upper fatty acid layer which may be recovered, for example, by decantation but in the case of acids of higher polarity it may be necessary to dilute the sulphonate salt in order to render the acids insoluble. Dilution of the acidified aqueous layer thus offers a simple and convenient method for separating out the liberated fatty acids. It will be appreciated that the use of a sufiiciently dilute mineral acid will achieve both acidification and dilution.
  • the residual aqueous solution may be discarded or recycled for further use since it contains the sulphonate salt.
  • the recycled aqueous solution also contains appreciable quantities of alkali-metal salts of the mineral acid used to liberate the fatty acids. The presence of excessive quantities of these salts may prove detrimental in the refining process and the amount present in the recycling aqueous solution is preferably main tained at a low level.
  • the fatty acid mixture obtained by acidification of the aqueous layer derived from the original alkali treatment is comparatively pure, it generally contains a residue of glyceride oil.
  • the process for recovering the fatty acids just described is modified so as to give a fatty acid of improved purity.
  • the aqueous layer derived from the original alkali treatment is boiled with at least sufficient alkali to hydrolyse the glyceride oil therein to give a further quantity of fatty acid soap and glycerol; the mixture is acidified with a mineral acid to hydrolyse the soap; the resulting mixture is allowed to form two layers; and the lower, aqueous layer is removed to leave a fatty acid layer of improved purity.
  • the aqueous layer used as starting material for this process contains the sulphonate salt originally present during the refining of the crude oil.
  • the presence of the sulphonate salt is essential to the success of the process since without it, boiling of the mixture would be a difiicult or impossible task owing to foaming caused by the soap, this foaming being wholly or largely prevented by the sulphonate salt.
  • All the alkali necessary for the process of the invention may be provided by adding a sufiicient excess of aikali in the original treatment of the raw glyceride oil.
  • alkali may be provided separately after the initial refining process.
  • the original oil and acid mixture may first be treated as before, but with approximately twice the amount of alkali required to saponify the acids present, in the presence of the sulphonate salt.
  • the resulting mixture separates into an upper purified oil layer and a lower aqueous layer, which contains the saponified acids, sulphonate salt, excess alkali and some entrained glyceride oil.
  • This aqueous layer is run off and boiled for about one hour. At this temperature and time the alkali present splits the glyceride oil. If necessary, further alkali may be added at this stage in order to give an excess calculated on the glyce-ride which is present.
  • the aqueous layer is then treated as before to liberate the fatty acids, and to recover the sulphonate salt solution, which may be recycled.
  • the refining factor is the proportion of the total weight of substance removed from the oil to the weight of free fatty acid originally present in the oil, and the ideal to be aimed at is a factor of unity.
  • EXAMPLE 1 100 parts of soya bean oil (acid value 2.2 mgs KOH/ g.) was heated to 95 C. To the hot oil was added 7 parts of sodium xylene sulphonate (SXS) in aqueous solution and an aqueous solution of caustic soda in an amount sufficient to give a excess based on the acid value of the oil. The amount of water in these solutions was enough to give a 40% solution of the SXS. The mixture was stirred and then allowed to settle. After 30 minutes the aqueous layer was separated, the oil was washed a second time with 30% SXS, separated, washed with water and then dried under vacuum at a temperature of 95 C.
  • SXS sodium xylene sulphonate
  • the refining factor may readily be calculated as follows:
  • the weight of substances removed from the oil when the SXS is present is 1.30 parts and the weight of free fatty acids in the original oil is 1.10 parts (half the acid value of 2.2 mg. KOH/g.).
  • method (i) relies on there being no more acid present in the system at the end of the refining procedure than at the start
  • method (ii) which relies only on measured quantities, applies, and shows that more acid is present at the end, i.e. hydrolysis has occurred during the refining.
  • the refined neutral oil in the conventional process still contains 0.13% fatty acid (the equivalent of an acid value of 0.25 mg. KOH/g.), only 0.85% (Ll-0.25) of the original fatty acid is transferred into the crude fatty acid. Since 3.16% of crude fatty acid is obtained, then 2.31% (3.16-0.85) of oil is entrained, either as acid produced by hydrolysis or as oil. Thus the loss of oil is even greater than at first sight appears, due to the relative inetficiency of the conventional deacidification.
  • the lower aqueous layer was separated, acidified to pH4 with 70% sulphuric acid and the separated acid oil washed with water and dried.
  • the neutral oil layer was washed twice with water and vacuum dried.
  • Crude snufiower seed oil (10,000 kg.) was treated at TABLE 3 50 C. with 60% phosphoric acld (100 kg.), the tem- Neutralon Acid Oil Refining perature ralsed to 90 during 30 minutes with stirring, and Y. m P m v P factor the mixture allowed to separate for 1 hour.
  • the aqueous i r ii (1% g.) A W l r i phase was discarded, the oil washed with water (400 kg),
  • Portion- A The degummed oil (5,000 kg.) was neutralised in the conventional manner at 70 C. with sodium hydroxide (67.2 kg. of 15% solution). The mixture was stirred for minutes after alkali addition then allowed to separate for four hours.
  • the aqueous soapstock layer was removed and the oil washed with water (200 kg.). It was necessary to repeat this operation a further 14 times to bring the soap content of the neutral oil below 0.05%.
  • Herring oil (5.65 %FFA) was used in the following examples.
  • the oil -('100 g.) was stirred at 90 C. with a solution of 34 g. of the sulphonate salt (equivalent to 6 FFA) together with 0.88 g. of sodium hydroxide (equivalent to 110% of theory) in water, (51 g. in Examples 14 and 15, 80 g. in Examples 16 and 17, corresponding to 40% and 30% solutions of sulphonate salt respectively).
  • the neutral oil had an FFA content of 0.08%.
  • the soapstock was acidified to pH4 with 70% sulphuric acid causing a separation of acid oil.
  • the acidic aqueous layer was run off, the acid oil was Washed with water kg.) and dried.
  • Portion B The degummed oil (5,000 kg.) was heated to 93 C. and treated, with stirring, with a solution of sodium hydroxide, (9.5 kg.) and Halvopon OR (202 kg.) in water (2885 kg). After stirring for 10 minutes the mixture was allowed to separate for 20 minutes.
  • the lower aqueous phase was run 011 and the neutral oil washed with water (3 X 200 kg.) giving a soap content in the oil of 0.04%.
  • the oil was vacuum dried and weighed, giving 4922 kg. with an FFA content of 0.06%.
  • the refining factor calculated as for A is 1.17.
  • the soapstock was treated as in A.
  • said salt is an alkali metal or ammonium salt of at least one sulphonic acid selected from the group consisting of benzene, xylene, toluene and cumene sulphonic acids, said salt being present in an amount between about 2 and 6 times the weight of the fatty acid present in said crude oil.
  • said salt is at least one sulphonic acid selected from the group consisting of benzene, xylene, toluene and cumene sulphonic acids, and wherein said sulphonic acid is present in an amount between about 40% and 60% of the weight of the water present.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US686832A 1962-06-27 1967-11-30 Method of refining vegetable and animal oils Expired - Lifetime US3440253A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB2466562A GB1002974A (en) 1963-01-21 1962-06-27 Method of refining vegetable and animal oils
GB259063 1963-01-21
OA52258A OA01864A (fr) 1965-11-19 1965-11-19 Procédé de raffinage d'huiles végétales et animales.

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US3440253A true US3440253A (en) 1969-04-22

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US (1) US3440253A (de)
DE (1) DE1235486B (de)
FR (1) FR1454709A (de)
MY (1) MY6600130A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8236977B2 (en) * 2009-05-04 2012-08-07 Primafuel Recovery of desired co-products from fermentation stillage streams
US9394505B2 (en) 2012-12-04 2016-07-19 Flint Hills Resources, Lp Recovery of co-products from fermentation stillage streams
CN111647460A (zh) * 2020-07-07 2020-09-11 甘肃华羚乳品股份有限公司 奶渣中稀奶油的精炼工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065249A (en) * 1961-04-07 1962-11-20 Repapis Manoli Process of refining fats and oils

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE528754C (de) * 1929-07-12 1931-07-03 I G Farbenindustrie Akt Ges Verfahren zur Entschleimung von pflanzlichen und tierischen OElen und Fetten
US2225575A (en) * 1938-06-04 1940-12-17 Refining Inc Process of refining glyceride oils
US2437075A (en) * 1945-01-05 1948-03-02 Clayton Benjamin Glyceride oil refining with foots softening agent
US2525702A (en) * 1948-10-22 1950-10-10 Benjamin Clayton Purification of oil
US2551496A (en) * 1949-09-19 1951-05-01 Procter & Gamble Process for refining cottonseed oil

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065249A (en) * 1961-04-07 1962-11-20 Repapis Manoli Process of refining fats and oils

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8236977B2 (en) * 2009-05-04 2012-08-07 Primafuel Recovery of desired co-products from fermentation stillage streams
US9169498B2 (en) 2009-05-04 2015-10-27 Edeniq, Inc. Recovery of desired co-products from fermentation stillage streams
US9394505B2 (en) 2012-12-04 2016-07-19 Flint Hills Resources, Lp Recovery of co-products from fermentation stillage streams
CN111647460A (zh) * 2020-07-07 2020-09-11 甘肃华羚乳品股份有限公司 奶渣中稀奶油的精炼工艺

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DE1235486B (de) 1967-03-02
FR1454709A (fr) 1966-02-11
MY6600130A (en) 1966-12-31

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